Trimethylol propane phosphite

ABSTRACT

WHERE R&#39;&#39;2 AND R&#39;&#39;3 ARE HYDROGEN, LOWER ALKYL OE PHENYL AND N&#39;&#39; IS ZERO OR 1, R3 IS H OR R1 AND N IS INTEGER OF 1 TO 100.   -C(-R&#39;&#39;2)(-R&#39;&#39;3)-   WHEREIN R&#39;&#39;1 IS HYDROGEN OR ALKYL, X IS O, S, SO2 OR   -(R&#39;&#39;1-CYCLOHEX-1,4-YLENE)-(X)N&#39;&#39;-(R&#39;&#39;1-CYCLOHEX-1,4-YLENE)-   AND THE POSITION ISOMERS THEROF AND WHERE R IS HYDROGEN OR ALKYL OF UP TO 20 CARBON ATOMS, R1 IS PHENYL, NAPHTHYL, ALKYL OF UP TO 20 CARBON ATOMS, HALO PHENYL, HALO NAPHTHYL, HALO ALKYL OF UP TO 20 CARBON ATOMS, ALKYL PHENYL OF UP TO 20 CARBON ATOMS IN THE ALKYL GROUP, ALKYL NAPHTHYL OF UP TO 20 CARBON ATOMS IN THE ALKYL GROUP, ALKENYL OF 3 TO 18 CARBON ATOMS, HALO ALKENYL OF 3 TO 18 CARBON ATOMS, OR BENZYL, AND WHERE THEHALO GROUP IS CL, BR OR I, R2 IS A HYDROGENATED DIHYDRIC PHENOL MOIETY HAVING THE FORMULA   P(-O-R1))N-R2-OH   HO-(R2-O-(5-R-1,3,2-DIOXAPHOSPHORINAN-2,5-YLENE)-CH2-O-   AND   R3 HO-(R2-O-(5-R-1,3,2-DIOXAPHOSPHORINAN-2,5-YLENE)-CH2-O)N-   1. PHOSPHITES OF THE FORMULAE

United States Patent 3,845,168 TRIMETHYLOL PROPANE PHOSPI-IITE AlvinGuttag, Bethesda, Md., assignor to Weston Chemical Corporation, NewYork, N.Y.

No Drawing. Application Jan. 16, 1970, Ser. No. 3,501, which is acontinuation-in-part of application Ser. No. 758,701, Sept. 10, 1968,now abandoned. Divided and this application Dec. 13, 1971, Ser. No.207,694

Int. Cl. C07f 9/08 US. Cl. 260-927 R 11 Claims ABSTRACT OF THEDISCLOSURE Phosphites, useful for stabilizing polymers, are provided ofthe formulae where n is at least 1, R is H or alkyl, R is aryl, alkyl,haloaryl, haloalkyl, alkaryl, alkenyl and haloalkenyl, R is ahydrogenated dihydric phenol moiety, R is H or R and Q is OCHz R P\C-CH2.

This is a division of application Ser. No. 3,501, filed Jan. 16, 1970,which in turn is a continuation-in-part of Ser. No. 758,701, filed Sept.10, 1968, now abandoned.

The present invention relates to novel phosphites.

It is an object of the present invention to prepare novel phosphites.

Another object is to develop novel stabilizers for hydrocarbon polymers,halogen-containing polymers, natural and synthetic rubbers and otherpolymers.

Still further objects and the entire scope of applicability of Shepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by preparingphosphites having the formula Where R is H or alkyl, R is aryl, alkyl,haloaryl, haloalkyl, alkaryl, alkenyl and haloalkenyl, R is ahydrogenated dihydric phenol moiety, R is H or R and n is an integer ofat least 1 and can be 10, 20 or even 100 or more.

sum.

The products of the invention of formula (la) may be prepared in severalfashions. Thus, a 1,3,2-dioxaphosphorinane of the formulae (1b) CHzOCHzO R-C P-O R or R-C PORi CH O CHzO CHzO H C H2O R;

is reacted with a hydrogenated dihydric phenol of the formula (3) HO-R-OH where R and R are as above and R is a hydrogenated dihydric phenolmoiety. For each repeating unit above 1, one less mole of the compoundof formula (3) is used than the number of moles of formula (2a) or (2b),when no end group reaction is desired. One additional mole of thecompound of formula (3) is required for each end group to be reacted.The reaction proceeds with the splitting out of either water and/or thecorresponding alcohol, R O=H for each repeating unit. The number ofmoles of R OH split out will increase by 2 for each additional repeatingunit above 1. Of course, the use of an appropriate number of additionalmoles of the hydrogenated dihydric phenol will be required to alsoprovide hydrogenated dihydric phenol end groups.

The compounds of formula (2a) may be prepared by reacting on amole-to-mole basis a trimethanol alkyl of the formula 1 4 CHz-OHR-C-CHz-OH CHz-OH where R, may be the same or different and as above andstopping the reaction when two moles of the corresponding alcohol orphenol, R OH are split off.

Alternately, the mono ethers of the trimethanol alkyls of formula (4)may be prepared and reacted with the compounds of formula (5) to providethe starting material of formula (2b) to make novel monomers. The ethersmay be made, for example, by reacting one mole of the compound offormula (4) with 1 mole of an alcohol of the formula R OH, where R is asabove, in the presence of an acid catalyst, e.g. sulfuric acid, andsplitting out 1 mole of water.

The phosphite of formula (1b) may be prepared by reacting the compoundof formula (2a) on a mole-tomole basis, with the phosphites of formula(5) and with splitting oif one mole of R OH to form the compounds of theformula:

( CHzO Or alternately a chlorophosphite may be reacted instead of thecompounds of formula e.g.

Thereafter the compounds of formula (6) are reacted with the compoundsof formula (3). For each repeating unit above 1, i.e. 2 or more, 1 lessmole of the compound of formula (3) is used than the number of moles offormula (6), when no end group reaction is desired. When end groupreaction is desired, 1 mole of the compound of formula (3) is requiredfor each end group. Again the number of moles of R OH split out wereincreased by 2 for each additional repeating unit above 1. The splittingout of R OH is preferably continued until a molecular weight of theproduct of about at least 1000 is obtained, e.g. 1000 to 30,000preferably 1500 to 4000 such as as 3000. Of course, the mole bases ofthe reaction may be varied depending upon the end groups desired. Whileformula (la) and (lb) are shown with end groups, those formulae areintended to also include, by definition, the same compounds but withoutany end groups or with at least one end group reacted.

Hence, if about 3 moles of the compounds of formula (3) are used forabout 2 moles of the compounds of formula (6) when four moles of R OHare split out the prod ucts formed are of the formula and R, R and R areas above. This corresponds to formula (1b) where n is 2 and each endgroup has been reacted. However, when additional moles of (3) and (6)are used, reactions between units across the other OR, group will occurand the triads of the formula Turning now to a more specific descriptionof the compounds used with the present invention R may be hydrogen andalkyl up to 20 carbon atoms, e.g. methyl, ethyl, propyl, hexyl, octyl,decyl, dodecyl, hexadecyl, octadecyl and eicosyl. R may be alkyl orhaloalkyl of up to 20 carbon atoms, e.g. methyl, ethyl, propyl, butyl,isobutyl, amyl, octyl, decyl, isodecyl, dodecyl, hexadecyl, octadecyl,eicosanyl, etc., and chloromethyl, chloroethyl, l-chloropropyl,chlorodecyl, chlorododecyl, bromohexadecyl and idooctadecyl, etc.Suitably the haloalkyl is a mono or disubstituted haloalkyl and thehalogen substituent is chlorine, bromine or iodine. The position of thehalo substitutent is not important and maybe in any position. Also R maybe aryl, alkaryl or haloaryl, with the alkyl substituent as describedabove, i.e. up to 20 carbon atoms, and again the halo atom or atomsbeing suitably a mono or disubstituted haloaryl, e.g. benzyl, naphthyl,phenyl, pmethyl phenyl, o-methyl phenyl, ethyl phenyl, m-propyl phenyl,hexyl phenyl, p-nonyl phenyl, dodecyl phenyl, poctadecyl phenyl, etc.,and the alkaryl being suitably a monor or disubstituted with halo asdescribed above. R also can be alkenyl, e.g. allyl, crotyl or oleyl.

For example, the 1,3,2 dioxaphosphorinanes may be 2 ethoxy 5 ethyl (5hydroxymethyl 1,3,2 dioxaphosphorinane). The 5 hydroxymethyl 1,3,2dioxaphosphorinane nucleus is designated as A and may also be 2 ethoxy 5methyl A, 2 ethoxy-S- propyl A, 2 ethoxy-S-hexyl A, 2-ethoxy-5-decyl A,2-ethoxy-5-dodecyl A, 2-ethoxy-5-octadecyl A, 2-ethoxy-5-chloromethyl A,2-ethoxy 5 bromoethyl A, 2-ethoxy-5-chlorohexyl A, 2-ethoxy 5 idooctylA, and the same compounds as above but instead of the 2-ethoxysubstituted dioxaphosphorinanes the 2 position may be substituted with,for example, a propoxy, decoxy, oetadecoxy, oleyloxy, chloroethoxy,chloropropoxy, bromodecoxy, and iodohexoxy, phenoxy, chloro or bromophenoxy, ethylphenoxy, hexylphenoxy, dodecylphenoxy,chloropentylphenoxy, bromododecylphenoxy, such compounds including2-phenoxy-5-ethyl A, 2 p nonylphenoxy-S-ethyl A, 2-oleyloxy 5 ethyl A,2-octa decyloxy-S-ethyl A, and the same compounds as above but theS-hydroxymethyl group may instead be the methoxy ether thereof with thesame substituents named above in the 2 position. Such compounds, ofcourse are produced from the reaction of the trimethanol alkyls offormula (4) which may be for instance trimethanol ethane, trimethanolpropane, trimethanol hexane, trimethor the position isomers thereof areproduced when the number of moles of R OH per repeating unit are splitout according to the following table.

ROH out (moles) Triads n Total Per "n" phite, decyl-dibutyl phosphite,methyl-diphenyl phosphite, ethyl-di phenyl phosphite, hexyl-di phenylphosphite, octadecyl-di phenyl phosphite, diphenyl oleyl phosphite,(diphenyl A9-octadecenyl phosphite), diethyl oleyl phosphite, diphenylstearyl phosphite (diphenyl octadecyl phosphite), dibutyl stearylphosphite, diphenyl hexadecyl phosphite, di-o-cresyl stearyl phosphite,triallyl phosphite, tricrotyl phosphite, dimethyl linoleyl phosphite,dimethyl stearyl phosphite, dimethyl oleyl phosphite, dimethyltetradecyl phosphite, dimethyl lauryl phosphite, dimethyl alpha naphthylphosphite, diphenyl beta naphthyl phosphite, diphenyl p-nonylphenylphosphite, diphenyl o-octadecylphenyl phosphite, diphenyl m-octadecenylphosphite (diphenyl oleyl phosphite), diphenyl 4 t butylphenylphosphite, diphenyl 2,4-dichlorophenyl phosphite, diphenylp-cyclohexylphenyl phosphite, triallyl phosphite, diphenyl 2,4-di(nonyl)phenyl phosphite, dimethyl 2,4 di (2,4-dibutyl) phenyl phosphite, tris2,4-xylenyl phosphite, tris 2,6-xylenyl phosphite.

Compounds such as dimethyl stearyl phosphite can be conveniently formedfor example by heating 1 mole of trimethyl phosphite with 1 mole ofstearyl alcohol, e.g. in the presence of a small amount of sodiummethylate and removing 1 mole of methyl alcohol. Compounds such asdiphenyl p-nonylphenyl phosphite can be formed in analogous fashion byheating 1 mole of triphenyl phosphite with 1 mole of p-nonylphenyl andremoving 1 mole of phenol per se.

As used in the present specification and claims, the term hydrogenateddihydric phenol signifies that all of the aromatic double bonds havebeen completely hydrogenated. Examples of hydrogenated dihydric phenolsused to form the products of the present invention are 4,4-isopropylidene dicyclohexanol (also called his (4 hydroxycyclohexyl)dimethyl methane or hydrogenated Bisphenol A), di (4-hydroxycyclohexyl)methane, di (4-hydroxycyclohexyl), bis (2-hydroxycyclohexyl) dimethylmethane, 1,4-dihydroxycyclohexane, di (4 hydroxy 3-methylcyclohexy1)dimethyl methane, di (4 hydroxy-3- methylcyclohexyl)methyl methane, di (4-hydroxy 3- methyl cyclohexyl) cyclohexyl methane,di (4-hydroxycyclohexyl) sulfone, di (4-hydroxycyclohexyl) sulfide, di(3-hydroxycyclohexyl) dimethyl methane, 4,4 methylene bis(2-methyl-6-t-butylcyclohexanol), di (4-hydroxycyclohexyl) ether1,3-dihydroxycyclohexane, di (3-chloro-4-hydroxycyclohexyl) dimethylmethane.

The preferred starting hydrogenated dihydric Phenols are bisphenol, themost preferred being hydrogenated Bisphenol A.

The l,3,2-dioxaphosphorinanes of formula (2a), (2b) may be prepared bythe reaction of the trimethanol alkyls of formula (4) with thetriphosphites of formula (5) at room temperature or lower or at aboveroom temperature, e.g. 20 to 100 C. and at atmospheric, superatmosphericor subatmospheric pressure, e.g. 5 mm. of Hg to 100 atmospheres.Preferably, however, the reaction is carried out under a vacuum of about14 mm. of Hg or less and at a temperature sufiicient to distill off thealcohol or water respectively, which is split out. Similarly, in formingthe compounds of formula (6) or the products of the invention by thereaction of formulae (2a), (2b) or (6) with the hydrogenated dihydricphenol of formula (3), the same conditions may be used, and also thevacuum and temperatures noted above are also preferred in order to moreeasily remove the alcohol or water split out.

It should also be noted that by choosing difierent substituents for R offormula (21b) or (6) or by choosing specific substituents for R offormula (2a) various position isomers of the products can be obtained.For example, when the R substituent on the methoxy group of (2b) is alower alkyl e.g. ethyl and the R substituent of phosphite moiety offormula (2b) is a higher alkyl or aryl, e.g. phenyl, the alcohol splitout between the R of the methoxy group and the OH group of thehydrogenated O-CI-IzORzO CH -C CH: O

CHzO reacted at a lower temperature before a second molecule of HO--R--OH reacted with a phenyl group at the ends of the molecule. However,if the positions on the ethyl and phenyl group are the reverse of theabove, the products formed would have the repeating units R CHrO OCHgCHgO O CH;

reacted at a lower temperature before the second molecule of HOR OHreacted with a phenyl group on the ends of the molecule. Further, when Ris the same, a mixture of position isomers will result. The samesituation is, of course, true for the product of formula (lb) as well asthe triads of formula (7).

Under the circumstances, by choosing the specific substituents for R onemay produce nearly pure products of only one of various position isomersor a mixture thereof as described. As is quite apparent, the particularsubstituents for R are chosen according to the boiling point of thealcohol (or phenol) split out at the pressure being used during thereaction.

In order to be concise in this specification and to not repeat detailsknown to the art, additional details of such reactions will be apparentfrom the disclosures of US. Pats. 3,341,629, 3,293,327; and 3,053,878,which disclosures are hereby incorporated by reference.

The reactions set forth above are all preferably catalyzed with 0.1 to5% based on the weight of the phosphite reactant or reactants of acatalyst which usually is a secondary phosphite, e.g., a dialkylphosphite, a diaryl phosphite or a dihaloaryl phosphite or an alkylinecatalyst. Examples of suitable catalysts are diphenyl phosphite, di(Z-methylphenyl) phosphite, di (4-dodecylphenyl) phosphite, di(4-octadecylphenyl) phosphite, di (2-chlorophenyl) phosphite, di (2,4dimethylphenyl) phosphite, di (4-bromophenyl) phosphite, diethylphosphite, dicyclohexyl phosphite, phenyl 3-rnethylphenyl phosphite,dioctadecyl phosphite, dimethyl phosphite, sodium phenolate, sodiumdecylate, potassium p-cresylate, sodium ethylate, sodium.octadeconolate, sodium hydride, sodium metal, potassium metal, lithimmethylate, sodium cetylate, trimethyl benzyl ammonium hydroxide andother quaternary ammonium hydroxides, sodium hydroxide, potassiumhydroxide.

The compounds of the present invention are useful as heat and lightstabilizers and as antioxidants. They appear to be more stable than thepolymers prepared in the Friedman Pat. No. 3,053,878.

They can be readily ground for incorporation in an amount of 0.01 to 20%into various polymers such as halogen containing resins, e.g. vinylchloride resins, as stabilizers against heat and light or asantioxidants. They are particularly useful in stabilizing rigidpolyvinyl chlorde resns where many other phosphites are unsuitable.

Examples of halogenated polymers which can be stabilized with thephosphites of the present invention include chlorinated polyethylenehaving about 14 to about e.g. 26% chlorine, polyvinyl chloride,polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride,polyvinylidene fluoride, polytetrafluoroethylene, copolymers ofvinylidene chloride and acrylonitrile (e.g. 80:20) or vinyl chloride(e.g. 85:15), copolymers of vinyl chloride with 1 to 90%, preferably 1to 40%, by weight of copolymerizable materials such as vinyl acetate,vinylidene chloride, vinylidene fluoride, diethyl fumarate, diethylmaleate and other alkyl fumarates and maleates, vinyl propionate, methylacrylate, ethyl acrylate, butyl acrylate, Z-ethylhexyl acrylate andother alkyl acrylates, methyl methacrylate, butyl methacrylate and othermethacrylates, methyl alpha chloroacrylate, styrene, vinyl ethyl ether,vinyl methyl ketone, acrylonitrile, allylidene diacetate,trichloroethylene, etc. Typical copolymers include vinyl chloride-vinylacetate (96:4), vinyl chloridevinyl acetate (87:13), vinylchloride-vinyl acetate-maleic anhydride (86:13:1), vinylchloride-vinylidene chloride (95:5), vinyl chloride-diethyl fumarate(95:5), vinyl chloride-trichloroethylene (95:5), vinylchloride-acrylonitrile (60:40), (80:20). They can also be used tostabilize resins where the halogen-containing component is present inminor amount, e.g. acrylonitrile-vinyl chloride copolymer (85:15) orhalogenated rubbers e.g. polychloroprene, chlorinated polyisobutylene,chlorinated natural rubber, chlorine containing polyurethanes, etc.

As is conventional in the art when the novel phosphites are employedwith halogen-containing resins, there can be added barium, cadmium andzinc salts and synergistic activity is noted in this connection, Thus,there can be included 0.5 to 10% of salts such as mixed bariumcadmiumlaurates, barium laurate, cadmium laurate, zinc stearate, cadmiumZ-ethyl hexoate, barium nonylphenolate, barium octylphenolate, bariumstearate, zinc octoate.

There can also be incorporated in the vinyl chloride resins and the like0.5 to 10% of organotin compounds, particularly sulfur-containingcompounds such as dibutyltin bis(octylthioglyco1late).

Conventional phenolic antioxidants can also be incorporated in an amountof 0.1 to 10%, e.g. 2,2-methylene bis (4-methyl-6-t-butylphenol),2,4,6-tri-t-butylphenol, 4,4'-isopropylidenephenol, etc.

The novel phosphites of the present invention can also be incorporatedin an amount of 0.01 to as stabilizers for hydrocarbon polymersincluding monoolefin polymers such as polyethylene polypropylene,ethylenepropylene copolymers (e.g. 80:20, 50:50, 20:80),ethylene-propylene terpolymers, e.g. ethylene-propylene-cyclooctadieneterpolymer, ethylene-butene-l copolymer, ethylene-decene-l copolymer,polystyrene, polyolefin, e.g. diolefin polymers such as natural rubber,rubbery butadiene styrene copolymers (75:25, 60:40), cis isoprenepolymer, polybutadiene, polyisobutylene, isobutylenebutadiene copolymer(butyl rubber, e.g. 97:3, 98.5:1.5). There can also be stabilized ABSrubbers and resins acrylonitrile-butadiene-styrene terpolymers, e.g.50:40:10).

They can be used in an amount of 0.01 to 20% to stabilize polyurethanes,(e.g. from toluene diisocyanate and polypropylene glycol molecularweight 2025), polyesters, e.g. Dacron (polyethylene terephthalate),polymeric tetramethylene terephthale isophthalate sebacate, orunsaturated polyesters, e.g. ethylene glycol-propylene glycoladipate-maleate molecular weight 5000 and the corresponding polymermodified with 10% styrene, nylon, e.g. polyhexamethylene adipamide,Delrin (polymerized oxymethylene) and Celcon (oxymethylene copolymer),polyvinyl butyral, polysulfones from conjugated diolefins, sulfurdioxide and a mono-ethylenically unsaturated compound, e.g. a terpolymerof butadiene, sulfur dioxide and styrene as set forth in Example 1 ofMostert Pat. No. 3,377,324, polycarbonates e.g. the reaction product ofBis-phenol A with phosgene or diphenyl carbonate as well as otherpolycarbonates set forth in Fritz Pat. No. 3,305,520.

vinyl chloride-2-ethylhexyl acrylate H When incorporated in hydrocarbonpolymers it is frequently advantageous to add conventional phenolicantioxidants as set forth above and conventional additives such asdiluryl thiodipropionate.

They are also useful as stabilizers for foods, oils, lubricants, andother products which deteriorate on oxidation.

The compounds of the invention are also useful as flame and fireproofing additives in polyurethane, hydrocarbon polymers, celluloseesters and ethers, e.g. cellulose acetate, methyl cellulose, ethylcellulose, cellulose acetate-propionate, etc.

The field of greatest utility at the moment, however, appears to be asstabilizers for rigid vinyl chloride resins. Since the compounds of thepresent invention are monomeric with readily defined'structures, it issurprising that they will act as stabilizers for rigid vinyl chlorideresins since the only phosphites previously found to satisfactorilystabilize rigid polyvinyl chloride are polymeric phosphites. The rigidpolyvinyl chloride resins normally do not contain over 10% plasticizerand can be completed devoid of plasticizer.

The invention will be illustrated by the following examples, but it isto be understood that the invention is not limited thereto but is fullyapplicable to the breadth of the foregoing disclosure. In the examplesall percentages and parts are by weight unless otherwise stated.

EXAMPLE 1 135 grams (1 mole) of trimethanol propane were heated to aboutC. with 310 grams (1 mole) of triphenyl phosphite and with 3 grams ofdiphenyl phosphite and subjected to vacuum distillation at 8 to 10 mm.until 188 grams (2 moles) of phenol were removed leaving a clear liquidin the pot. The reaction mixture was cooled by blowing nitrogen throughthe pot and then fractionated. The 2-phen0xy, S-ethyl,S-hydroxymethyl-1,3,2-dioxaphosphorinane was recovered. The product hadthe formula EXAMPLE 2 514 grams (2 moles) of the 2-phenoxy, 5-ethyl,S-hydroxymethyl 1,3,2-dioxaphosphorinane of Example 1 and 480 grams (2moles) of hydrogenated bis-phenol A were heated at increasingtemperatures in the presence of 5 grams of diphenyl phosphite as acatalyst while being subjected to vacuum distillation at 5 to 10 mm.until about 2 moles of phenol and 1 mole of water were distilled off.The residue in the pot was about 714 grams of viscous liquid producttogether with the diphenyl phosphite catalyst. The catalyst was removedby vacuum fractionation to yield the purified product of the formula of(la) where R2 iS- R is --CH CH and R is H and n is 2.

EXAMPLE 3 The procedure of Example 1 was repeated replacing thetrimethanol propane with trimethanol decane and the corresponding5-nonyl dioxaphosphorinane was recovered.

EXAMPLE 4 The 5-nonyl dioxaphosphorinane of Example 3 was used in theprocedure of Example 2 to replace the 5-ethyl dioxaphosphorinane andproduced the product of Example 2 except that R is octyl.

9 EXAMPLE The procedure of Example 2 was repeated replacing the 5-ethyldioxaphosphorinane with the 5-chloropropyl dioxaphosphorinane andproduced the product of Example 2 except that R is chloropropyl.

EXAMPLE 6 The procedure of Example 1 was repeated except the trimethanolpropane and triphenyl phosphite was replaced with the followingreactants:

CH2OH /OR1 RCGH20H and P-O R1 CHzOH O R;

where R is: where R] is:

( C a phenyl C a( z)5 p y (C) CHzCl(CHz)odecyl 2 -z)m nonyl phenylEXAMPLE 7 The reaction products of Example 6, i.e. (A), (B), (C) and (D)were serially reacted with the hydrogenated bisphenol A according to theprocedure of Example 2. All of the products obtained were viscousliquids.

EXAMPLE 8 257 grams (1 mole) of 2-phenoxy, 5-ethyl-5-hydroxymethyl1,3,2-dioxaphosphorinane was heated at increasing temperatures with 310grams (1 mole) of triphenyl phosphite and 3 grams of diphenyl phosphiteunder a vacuum of 5 to 10 mm. until 94 grams (1 mole) of phenol wereremoved. The reaction mixture was then cooled and vacuum fractionated torecover purified the 2-phenoxy-5-(diphenyl phosphite methoxy)-5 ethyl,1,3,2-dioxaphosphorinane product of the formula CHIO EXAMPLE 9 950 grams(2 moles) of the product of Example 8 were heated at increasingtemperatures with 600 grams (2.5 moles) of hydrogenated bis-phenol Aunder 8 to 12 mm. vacuum and with 6 grams of diphenyl phosphite untilapproximately 185 grams (approximately 2.5 moles) of phenol weredistilled off. The cooled product was a glassy solid and had the formulaof (lb) where R; is

R is phenyl, R is CH CH and n is 4.

EXAMPLE 10 inane and 2-phenoxy-5 (dichlorodecyl phosphite methoxy) 5ethyl 1,3,2-dioxaphosphorinaue.

EXAMPLE 11 Each of the products of Example 10 were serially reacted withbis-phenol A and the corresponding products were obtained. Each productobtained was a glassy highly viscous semi-solid.

EXAMPLE 12 2 moles of 2-phenoxy-5-(diphenyl phosphite methoxy)- 5 ethyl,1,3,2-dioxaphosphorinane was heated with 3.2 moles of hydrogenatedbis-phenol A under a vacuum of 8 to 12 mm. and with 8 grams of diphenylphosphite until 4 moles of phenol was distilled off. The product had theformula The procedure of Example 12 was repeated but using 8 moles ofthe phosphorinane and 12.8 moles of the hydrogenated bis-phenol A andsplitting out 19 moles of phenol. The product had the formula Theprocedure of Example 13 was repeated with 20 moles of the phosphorinaneand 32 modes of hydrogenated bisphenol A with 49 moles of phenol beingsplit out.

The product was a hard glassy solid with the formula as in Example 13except it was 8.

1 1 EXAMPLE 1s The procedure of Example 12 was repeated except thatthere is used 2 moles of 2-phenoxy-5-(phenyl,p-nonyl phenyl phosphitemethoxy)-5 ethyl, 1,3,2-dioxaphosphorinane with 3.2 moles ofhydrogenated bisphenol A. The product is a glassy solid having pendantp-nonylphenyl groups.

EXAMPLE 16 The procedure of Example 12 was repeated except there is used2 moles of Z-phenoxy-S-(phenyl, stearyl phosphite methoxy) 5ethyl,l,3,2-dioxaphosphorinane with 3.2 moles of hydrogenated bisphenolA. The product is a glassy solid having pendant stearyl groups.

EXAMPLE 17 The procedure of Example 12 is repeated except that 2 molesof 2 phenoxy 5 (phenyl, isodecyl phosphitemethoxy)-5-ethyl,1,3,2-dioxaphosphorinane is used with 3.2 moles ofhydrogenated bisphenol A. The product is a glassy solid.

EXAMPLE 18 1 part of the product of Example 12, 2 parts of bariumcadmiumlaurate and 100 parts of rigid polyvinyl chloride were ground and mixedtogether with heating. The mixed resin showed good stabilization.

EXAMPLE 19 1 part of the product of Example 13, together with 2 parts ofcalcium stearate were milled into 100 parts of polyvinyl chloride and 50parts of dioctyl phthalate to give a stabilized product.

EXAMPLE 20 1 part of the product of Example 14 was heated on a mill andmilled into 100 parts of polyvinyl chloride, 50 parts of dioctylphthalate and 2 parts of calcium stearate to give a stabilized product.

EXAMPLE 21 The procedure of Example 12 is repeated except that 2 molesof 2-phenoxy-5-(phenyl, oleyl phosphite methoxy)- 5- ethyl,1,3,2-dioxaphosphorinane is used with 3.2 moles of hydrogenatedbisphenol A. The product is a glassy solid having pendant oleyl groups.

As will be appreciated, the hydrogenated dihydric phenol residue of thepresent phosphites may have the formula where R' is hydrogen or alkyl, Xis O, S, S0 or where R' and R' are hydrogen, lower alkyl or phenyl and nis zero or one.

As noted above, the mole ratios of the reactants may vary depending uponthe end groups reacted. Hence, with regard to formula (1a) if 1 mole offormula (2b) is reacted with 1 mole of formula (3) the product will be:

HO-RzO-P C-CH2O R1.

However, if 2 moles of (2b) are reacted with 1 mole of (3) the productwill be OCH: R OCH: R Rio-P C-CHzO-RzO-P C-CHzORi 0cm OOH:

with no end group reacted. The results will be similar in the reactionto produce the products of formula (lb) or 12 (7). Likewise, if 2 molesof (2b) are reacted with 2 moles of (3) one end group will be CH OR OHor if 3 moles of (3) are reacted each end group will be likewiseterminated by --OH. Hence all of these combinations are included, bypresent definition in the formulae of the products, noted above.

Also, as can be appreciated, the number of moles of R OH split out willdepend on the number of repeating units and the number of end groupsreacted. For example, when formula (6) is reacted with formula (3) andno end group reaction is desired, the moles will be as follows:

Moles of Moles of Moles of Increase in No. of repeating formula formulaRiOH mole of R1011 units (6) (3) split for add. unit However, if one endgroup is to be reacted, the moles of formula (3) must be increased by 1or if both end groups are to be reacted, the moles of formula (3) mustbe increased by 2. Of course, the moles of R OH split out will alsoincrease by 1 or 2, respectively. In other words, the number of moles ofR CH split out will be 2 times the number of moles of formula 3) used informing the repeating units plus 1 additional mole of R OH for each endgroup reacted. An analogous situation exists for each of the products ofthe invention.

What is claimed:

1. Phosphites of the formulae and the position isomers thereof and WhereR is hydrogen or alkyl of up to 20 carbon atoms, R is phenyl, naphthyl,alkyl of up to 20 carbon atoms, halo phenyl, halo naphthyl, halo alkylof up to 20 carbon atoms, alkyl phenyl of up to 20 carbon atoms in thealkyl group, alkyl naphthyl of up to 20 carbon atoms in the alkyl group,alkenyl of 3 to 18 carbon atoms, halo alkenyl of 3 to 18 carbon atoms,or benzyl, and where the halo group is Cl, Br Or I, R is a hydrogenateddihydric phenol moiety having the formula wherein R' is hydrogen oralkyl, X is O, S, S0 or where R and R, are hydrogen, lower alkyl orphenyl and n is zero or 1, R is H or R and n. is integer of 1 and theposition isomers thereof and where Q is OCH: R

OCHa n is to 100 and R is hydrogen or alkyl of up to 20 carbon atoms, R,is phenyl, naphthyl, alkyl of up to 20 carbon atoms, halo phenyl, halonaphthyl, halo alkyl of up to 20 carbon atoms, alkyl phenyl of up to 20carbon atoms in the alkyl group, alkyl naphthyl of up to 20 carbon atomsin the alkyl group, alkenyl of 3 to 18 carbon atoms, halo alkenyl of 3to 18 carbon atoms or benzyl, and where the halo group is Cl, Br or I, Ris a hydrogenated dihydric phenol moiety having the formula where R; ishydrogen or alkyl, X is O, S, S0, or

l I R: where R, and R; are hydrogen, lower alkyl or phenyl and n' iszero or 1.

3. The phosphites of claim 1 wherein the phenol moiety is hydrogenatedbis-phenol A.

4. The phosphites of claim 2 wherein the phenol moiety is bis-phenol A.

5. The phosphites of claim 1 formula (1) where R is i @r@- OH: R is CHCH R is H, and n is 2.

14 6. The phosphites of claim 1 formula (2) wherein R, is

10. A phosphite according to claim 1 having formula (2).

11. A composition according to claim 1 where n of formula (2) is equalto 2.

References Cited UNITED STATES PATENTS 3,576,917 4/1971 Friedman 260927R 3,576,918 4/1971 Rattenbury 260927 R 3,576,919 4/1971 Rattenbury260927 R LORRAINE A. WEINBERGER, Primary Examiner R. L. RAYMOND,Assistant Examiner US. Cl. X.R. 26045.7 P, 937

1. PHOSPHITES OF THE FORMULAE